Multilayered structures

ABSTRACT

A novel multilayer structure in which one layer comprises a polymer comprising a solventless, waterless, melt-processable acrylonitrile olefinically unsaturated polymer and the other layer comprises an organic polymer. Either polymer can be employed as the inner layer or the outer lays component of the multilayer structure.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims the benefit of priorityunder 35 U.S.C. § 120 for U.S. application Ser. No. 11/396,614 filed onApr. 4, 2006, which is a continuation of U.S. patent application Ser.No. 09/607,002, filed Jun. 29, 2000, which in turn is a divisional ofU.S. application Ser. No. 08/989,807, filed Dec. 12, 1997, nowabandoned, the disclosures of which are incorporated herein by referencein their entirety and to which priority and benefit under 35 U.S.C. §120 is claimed to applications.

BACKGROUND OF THE INVENTION

The present invention relates to multilayer structures and methods fortheir preparation. Mote particularly, the invention relates to amultilayer structure having typical organic polymer layer(s) anddissimilar organic polymer layer(s) comprising a solventless waterlessmelt-processable acrylonitrile olefinically unsaturated polymer. It isunderstood that the term multilayer structure includes film, tape,sheets, containers, composites, articles that are extruded,injection-molded, compression molded m the like, structural body, andthe like throughout this specification.

No single polymer is capable of providing the chemical and physicalproperties that are required for various applications. It is useful tomanufacture films, sheets, containers and packages from multilayerpolymer materials because different polymer compositions providedifferent properties, and by combining different polymer layers thefinal product will have the benefit of the different polymer properties.Unfortunately, polymers that provide one kind of properties do notreadily combine or adhere to polymers that provide other unique chemicaland physical properties.

Therefore, it would be advantageous to produce a multilayer materialusing dissimilar polymer layers. The present invention produces such amultilayer material. It would be further advantageous to produce amultilayer structure with an acrylonitrile olefinically unsaturatedpolymer. An acrylonitrile olefinically unsaturated polymer can becharacterized by high resistance to abrasion, solvents, gas and UVlight, hardness and high puncture resistance but lower water vaporresistance rate in comparison to other polymers such as polyolefins. Anorganic polymer can be characterized by high water vapor resistancerate, high tear strength, good heat seal and reduced shrink propertiesand low density, but has poor gas and solvent barrier properties and lowUV resistance. The unique nitrile and organic polymer multilayerstructure of the present invention provides improved gas/water barrierproperties, resistance to chemicals, abrasion, solvents, and UV lightimproved rigidity, weatherability, wear performance and impact strength.These and other advantages will become apparent as the description ofthe invention proceeds.

SUMMARY OF THE INVENTION

The present invention is directed to a multilayer structure whichdisplays improved resistance to abrasion, organic solvents, water vapor,gas (i.e., oxygen, carbon dioxide barrier properties), and UV light, aswell as improved rigidity, impact strength, and wear performance. Themultilayer structure comprises an organic polymer layer; and asolventless, waterless, melt processable acrylonitrile olefinicallyunsaturated polymer layer which comprises about 50% to about 95% byweight polymerizable acrylonitrile monomer and at least one of about 5%to about 50% by weight polymerizable olefinically unsaturated monomer.

The present invention also provides a method for preparation of themultilayer structure which comprises the steps of providing an organicpolymer; providing a solventless, waterless, melt-processableacrylonitrile olefinically unsaturated polymer comprising about 50% toabout 95% by weight polymerizable acrylonitrile monomer and at least oneof about 5%, to about 50% by weight polymerizable olefinicallyunsaturated monomer, and melt processing the polymeric components. Thepresent invention may be used in a variety of molding methods, includingextrusion, co-injection molding, multilayer extrusion molding,multilayer blow molding, injection molding, compression molding and thelike.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, the multilayer structurecomprises an organic polymer layer and a waterless, solventlessmelt-processable acrylonitrile olefinically unsaturated polymer(hereinafter “acrylonitrile olefinically unsaturated polymer”) layer.The multilayer structure comprises at least two layers.

The layer of organic polymer includes, but is not limited to, syntheticand natural polymers. The synthetic polymer includes, but is not limitedto, polyolefins such as polypropylene, polyethylene andpoly(4-methylpentene-1); polyesters such as polyethylene terephthalate(PET), polybutylene terephthalate (PBT), and polyethylene naphthalate(PEN); polyamides (PA), including aliphatics and aromatics, such asnylons; polycarbonates such as polybisphenol-A carbonate (PC);polyimides (PI) such as polyetherimide aliphatic and aromatic;poly(amide-imides); poly(ester-imides); polystyrenes (PS);polyurethanes; polyvinyl chloride (PVC); polyketones; polyphenyleneoxide (PPO); polyvinyl alcohol (PVA); polysulphone; liquid crystallinepolymers such as copolyesters of hydroxy-benzoic acid with 2,6 naphthoicacid (Vectra); Kevlar® (available from DuPont); acrylonitrile containingpolymers including a waterless, solventless melt processableacrylonitrile olefinically unsaturated polymer or an acrylonitrilecontaining polymer that is soluble in a solvent; and the like.

The monomers employed in the organic polymer can be one monomer or acombination of monomers dependent upon the properties desired to impartto the end use of the multilayer structure. In a multilayer structure ofthree layers or more, the organic polymer is employed as either theouter layer m the inner layer of the structure, but not both.

The other polymer layer is an acrylonitrile olefinically unsaturatedpolymer comprising an acrylonitrile monomer polymerized with at leastone olefinically unsaturated monomer. The acrylonitrile olefinicallyunsaturated polymer comprises about 50% to about 95% by weight,preferably about 75% to about 93% by weight, and most preferably about85% to show 92% by weight of polymerized acrylonitrile monomer, and atleast one of about 5% to about 50% by weight, preferably about 7% toabout 25% by weight, and most preferably about 8% to about 15% by weightof polymerized olefinically unsaturated monomer. The acrylonitrileolefinically unsaturated polymer is employed as the outer layer or theinter layer or both.

The olefinically unsaturated monomer employed is one of more ofolefinically unsaturated monomer with a C═C double bond polymerizablewith an acrylonitrile monomer. The olefinically unsaturated monomer canbe a single polymerizable monomer resulting in a co-polymer, or acombination of polymerizable monomers resulting in a multi-polymer. Thechoice of olefinically unsaturated monomer or a combination of monomersdepends upon the properties desired to impart to the resultingmultilayer structure and its end use.

The olefinically unsaturated monomer generally includes, but is notlimited to, acrylates such as methyl acrylates and ethyl acrylates;methacrylates, such as methyl methacrylate; acrylamides andmethacrylamides and each of their N-substituted alkyl and arylderivatives, such as acrylamide, methactylamide, N-methylacrylamide,N,N-dimethyl acrylamide; maleic acid and its derivatives, such asN-phenylmaleimide; vinylesters, such as vinyl acetate; vinylethers, suchas ethyl vinyl ether and butyl vinyl ether, vinylamides, such as vinylpyrrolidone, vinylketones, such ethyl vinyl ketone and butyl vinylketone; styrenes, such as methylstyrene, styrene and indene; halogencontaining monomers, such as vinyl chloride, vinyl bromide, andvinylidene chloride; ionic monomers, such sodium vinylsulfonate, sodiumstyrenesulfonate, and sodium methyl sulfonate; acid containing monomerssuch as itaconic acid, styrene sulfonic acid and vinyl sulfonic acid;base-containing monomers, such as vinyl pyridine,2-aminoethyl-N-acrylamide, 3-aminopropyl-N-acrylamide,2-aminoethylacrylate, 2-aminoethymathacrylate; and olefins, such aspropylene, ethylene, isobutylene.

The multilayer structure is a minimum of two layers, or an unlimitednumber of layers, depending on the end use application. For example, athree-layer structure employs an inner layer of either the organicpolymer or the acrylonitrile olefinically unsaturated polymer with theinner layer sandwiched therebetween the outer layers which is theorganic polymer or the acrylonitrile olefinically unsaturated polymer,depending on the desired end use of the product.

The polymer employed as the inner layer has a dissimilar composition ora dissimilar molecular weight or dissimilar theological properties incomparison to the polymer employed as the outer layer. The organicpolymer and the acrylonitrile olefinically unsaturated polymer arethermally stable in relationship to each other. The organic polymer orthe acrylonitrile olefinically unsaturated polymer is either the innerlayer or the outer layer of the multilayer structure depending on theend use application and on the chemical and physical properties of thepolymers such as melt flow and thermal characteristics, molecularweight, composition and the like. In the invention, the polymer employedas the inner layer of the multilayer structure is in the range of about1% weight to about 99% weight, preferably about 5% weight to about 95%weight and more preferable about 10% weight to about 90% weight of themultilayer structure. The polymer employed as the otter layer in themultilayer structure is in the range of about 99% weight to about 1%weight, preferably about 95% weight to about 5% weight and morepreferable about 90% weight to about 10% weight of the multilayer. Theminimum amount of polymer for a layer is such that the polymer of theadjacent layer is not excessively exposed on the surface.

The composition of the polymer used for the outer layer and thecomposition of the polymer used for the inner layer are preparedseparately. The acrylonitrile olefinically unsaturated polymer isprepared by known polymerization processes. An exemplary, method to makethe melt-processable high-nitrile multi-polymer is described in U.S.Pat. No. 560,222 entitled “A Process for Making a Polymer ofAcrylonitrile/Methacrylonitrile/Olefinically Unsaturated Monomers” andU.S. Pat. No. 5,618,901 entitled “A Process for Making a High NitrileMultipolymer Prepared from Acrylonitrile and Olefinically UnsaturatedMonomers,” both incorporated herein by reference. The organic polymer isprepared by known polymerization processes.

The multilayer structure is produced by a melt process. The thickness ofthe layers depend on the desired end use and is in the range of about 1micron to any thickness depending on the end use application. The meltprocessing temperature is dependent on the melt temperature and thethermal degradation temperature of the composition of the outer layerpolymer and the inner layer polymer.

The acrylonitrile olefinically unsaturated polymer is melt processed ina waterless, solventless system; however trace amounts of water as animpurity may exist up to 3%, preferably 1% or less. A process forproducing the multilayer structure of this invention comprises preparingseparately the organic polymer and the acrylonitrile olefinicallyunsaturated polymer; combining the components; and extruding the polymercomponents through conventional means.

In a one-step injection molding process, the various melt polymercomponents are combined in a mold and the mold allowed to cool.

In a one-step extrusion process, the various melt polymer components arecoextended in a conventional manner.

Additional treatment may be employed to further modify thecharacteristics of the multilayer structure by the addition ofreinforcement materials such as carbon fibers, glass fibers and thelike; additives; Mustering agents; coloring agents and the like. It isunderstood that any additive possessing the ability to function in sucha manner can be used so long as it does not have a deleterious effect onthe properties of the nitrite multilayer structure. The invention is notlimited to any specific lamination, extrusion, injection or moldingtechniques.

These multilayer structures are used for packaging applications,subsequent fabricated articles prepared from sheet precursors. Inparticular, the multilayer structures are used as films, packagingfilms, tapes, sheets, pipes, packages, trays, bottles, containers,composites, fabricated articles, structural bodies and the like.Further, the multilayer structure is employed in packaging applications,including automotive fuel tanks, as well as containers including thosethat can go from hot filling to freezer to microwave, buildingmaterials, pipes and the like.

SPECIFIC EMBODIMENT

The following examples demonstrate the advantages of the presentinvention. The polymers used were: 1) acrylonitrile olefinicallyunsaturated polymer crumb employing 85% acrylonitrile monomerpolymerized with 15% methyl acrylate polymer; and 2) an organic polymerof polypropylene pellets (melt index=18) with an 18 melt flow index orpolyethylene polymer pellets with high density and a 1 melt flow index.

The acrylonitrile methyl acrylate polymer and polyolefin of eitherpolypropylene or polyethylene were mixed together in a one gallon pail.The mixture was extruded using a three zone, 0.75 inch extruder fittedwith a film (tape) die. The mixture of polymer resin was added to ahopper and extruded at about 35 rpm. The material coming out of the diewas taken up on a film (tape) machine comprising two rollers. Therollers could optionally be heated. The rollers were compressed toregulate the thickness of the film (tape) and the speed of the rollerswas adjusted to regulate the thickness and width of the film (tape). Theresulting multilayer structure was three layers in a sandwichconfiguration. The following Table I describes the ratios of eachpolymer and condition employed. PP stands for polypropylene; PE standsfor polyethylene; and AMLON™ stands for acrylonitrile olefinicallyunsaturated polymer employing 85% acrylonitrile copolymerized with 15%methyl acrylate.

Ratio Extruder Temps Film Roll Speed 100PP (comparison) 215/215/215/215°C. 7.0 100 AMLON ™ (comparison) 215/215/215/215° C. 7.0 80 PP/20 AMLON ™215/215/215/215° C. 7.0 70 PP/30 AMLON ™ 215/215/215/215° C. 5.5 50PP/50 AMLON ™ 225/225/225/225° C. 6.0 20 PP180 AMLON ™ 235/235/235/235°C. 3.0 50 PP/50 AMLON ™ 200/200/200200° C. 80 PE/20 AMLON ™215/215/215/215° C. 4.0

The composite tapes were examined by optical microscopy using a Leitzcross polarizing optical microscope (Laborlux 12 pol) equipped with aMettler hot stage. It was determined by optical microscopy that the tapehad a multilayer configuration.

FIG. 1( a) shows the morphology of an acrylonitrile methyl acrylateextruded tape which is used for a comparison.

FIG. 1( b) shows the morphology of an acrylonitrile methylacrylate/polypropylene 8020 extruded tape.

FIG. 1( c) shows the morphology of an acrylonitrile methylacrylate/polypropylene 50/50 extruded tape.

FIG. 1( d) shows the morphology of an acrylonitrile methylacrylate/polypropylene 20180 extruded tape.

FIG. 1 demonstrates that the acrylonitrile methyl acrylate/polypropylenelaminar morphologies are obtained from a large range of different ratiosof polymer.

FIG. 2( a) shows the morphology of an acrylonitrile methyl acrylateextruded tape which is used for comparison.

FIG. 2( b) shows the morphology of a polypropylene extruded tape whichis used for comparison.

FIG. 2( c) shows the morphology of an acrylonitrile methylacrylate/polypropylene 30/70 extruded tape.

FIG. 2( d) shows the morphology of an acrylonitrile methylacrylate/polypropylene 20/80 extruded tape.

FIG. 2 demonstrates that the extruded tapes were in a sandwichconfiguration with the polypropylene as the inside layer and theacrylonitrile methyl acrylate as the outside layers. This isdemonstrated by the pictures which show in FIG. 2( a) that theacrylonitrile methyl acrylate has crystallites too small in size m bedistinguished by optical microscopy in comparison to FIG. 2( b)polypropylene which exhibits a distinct crystalline pattern. Thiscrystalline structure, is not observed for FIGS. 2( c) and (d) whichindicates that the acrylonitrile methyl acrylate is present as bothoutside layers, while the polypropylene forms the inside layer.

FIGS. 3( a) and (b) show the morphology of an acrylonitrile methylacrylate/polypropylene 50/50 extruded tape.

FIGS. 3( c) and (d) show the same tape after extraction with DMF(dimethylformamide) for about 40 hours at room temperature. FIG. 3demonstrates that before extraction the morphology of the 50/50acrylonitrile methyl acrylate (polypropylene extruded tape is laminar,with acrylonitrile methyl acrylate present as the outside layers. Afterextraction with the DMF, the acrylonitrile methyl acrylate layer isremoved, and the polypropylene crystalline pattern is readily observed.

FIGS. 4( a) and (b) show the morphology of an acrylonitrile methylacrylate/polyethylene 20/80 extruded tape and FIGS. 4( c) and (d) showthe same tape after extraction with DMF for about 40 hours at roomtemperature. FIG. 4 indicates that the laminar morphology is alsocharacteristic for acrylonitrile methyl acrylate/polyethylenecombinations. It also demonstrates that in this case the polyethylene ispresent as the outside layers, because after the DMF extraction, themorphology of the extruded tape remains unchanged.

From the above description and examples of the invention, those skilledin the art will perceive improvements, changes, and modifications in theinvention. Such improvements, changes and modifications within thoseskilled in the art are intended to be covered by the appended claims.

1. A non-laminated multilayer structure, said structure comprising: alayer having an organic polymer composition; and in direct contacttherewith, a layer having a solventless, waterless, melt-processableacrylonitrile olefinically unsaturated polymer comprising about 50% toabout 95% by weight polymerizable acrylonitrile monomer and at least oneof about 5% to about 50% by weight polymerizable olefinicallyunsaturated monomer, wherein the organic polymer and the acrylonitrileolefinically unsaturated polymer are thermally stable in relationship toeach other.
 2. The non-laminated multilayer structure of claim 1,wherein the acrylonitrile olefinically unsaturated polymer is positionedbetween two layers of the organic polymer and wherein the organicpolymer for each layer is the same or substantially similar polymercomposition.
 3. The non-laminated multilayer structure of claim 1,wherein the organic polymer is positioned between two layers of theacrylonitrile olefinically unsaturated polymer wherein saidacrylonitrile olefinically unsaturated polymer for each layer is thesame or substantially similar polymer composition.
 4. The non-laminatedmultilayer structure of claim 1, wherein the olefinically unsaturatedmonomer is selected from a group consisting of methyl acrylates, ethylacrylates, acrylamides and methyl acrylamides and each of theirsubstituted alkyl and aryl derivatives, maleic acid and its derivatives,vinylesters, vinylethers, vinylamides, vinylketones, styrenes,halogen-containing monomers, ionic monomers, acid-containing monomers,base-containing monomers, olefins and combinations thereof.
 5. Thenon-laminated multilayer structure of claim 4, wherein the olefinicallyunsaturated monomer is selected from the group consisting of methylmethacrylate, acrylamide, methacrylamide, N-methylacrylamide,N,N-dimethyl acrylamide, N-phenyhmaleimide; vinyl acetate, ethyl vinylether and butyl vinyl ether, vinyl pyrrolidone, ethyl vinyl ketone,butyl vinyl ketone, methylstyrene styrene, indene, vinyl chloride, vinylbromide, vinylidene chloride, sodium vinylsulfonate, sodiumstyrenesulfonate, sodium methyl sulfonate, itaconic acid, styrenesulfonic acid, vinyl sulfonic acid, vinyl pyridine,2-aminoethyl-N-acrylamide, 3-aminopropyl-N-actylamide,2-aminoethylacrylate, and 2-eminoethymethacrylate, propylene, ethylene,isobutylene and combinations thereof.
 6. The non-laminated multilayerstructure of claim 1, wherein said organic polymer is selected from thegroup consisting of polyolefins, polyesters, polymides, polycarbonates,polyamides, polyamide imides, polyester-imides, polystyrenes,polyurethanes, polyvinyl chloride, polyvinyl alcohol, polyketones,polyphenylene oxide, polysulphone, acrylonitrile-containing polymers,liquid crystalline polymers, cellulosic, wood, silk, cotton andcombinations thereof.
 7. The non-laminated multilayer structure of claim6, wherein the organic polymer is selected from the group consisting ofpolypropylene, polyethylene, poly(4-methylpentene-1), polyethyleneterephthalate, polybutylene terephthalate, polyethylene naphthalate,nylon, polybisphenol-A carbonate; polyetherimide, copolyester ofhydroxyl-benzoic acid with 2,6 naththoic acid, solventless, waterless,melt-processable acrylonitrile containing polymers and combinationsthereof.
 8. A film formed from the non-laminated multilayer structure ofclaim
 1. 9. A pipe formed from the non-laminated multilayer structure ofclaim
 1. 10. A tape formed from the non-laminated multilayer structureof claim
 1. 11. A container formed from the non-laminated multilayerstructure of claim
 1. 12. A bottle formed from the non-laminatedmultilayer structure of claim
 1. 13. A sheet formed from thenon-laminated multilayer structure of claim 1.